초록
The structures of $Tl_{12-2x}Zn_x-A$ (x = 4.3 and 3.25), vacuum dehydrated zeolite A with all $Na^+$ ions replaced by $Tl^+$ and $Zn^{2+}$ as indicated, have been determined by single-crystal X-ray diffraction techniques in cubic space group Pm3m at 21(1) $^{\circ}C$ (a=12.100(2) ${\AA}$ for $Tl_{3.4}Zn_{4.3}-A$ and a=12.092(2) ${\AA}$ for $Tl_{5.5}Zn_{3.25}-A$). The crystals of $Tl_{3.4}Zn_{4.3}-A$ and $Tl_{5.5}Zn_{3.25}-A$ were prepared by flow method using exchange solutions in which mole ratios of $TlNO_3$,/TEX> and $Zn(NO_3)_2$ were 1:50 and 1:1, respectively, with total concentration of 0.05 M. The structures of the dehydrated $Tl_{3.4}Zn_{4.3}-A$ and $Tl_{5.5}Zn_{3.25}-A$ were refined to yield the final error indices $R_1$ = 0.075 and $R_2$ = 0.075 with 236 reflections, and $R_1$ = 0.057 and $R_2$ = 0.064 with 202 reflections, respectively, for which I > 3$\sigma$(I). Both structures indicate that Zn(II) ions are coordinated by three framework oxygens: the Zn(II) to O(3) distances are 2.08(1) ${\AA}$ for $Tl_{3.4}Zn_{4.3}-A$ and 2.07(1) ${\AA}$ for $Tl_{5.5}Zn_{3.25}-A$, respectively. In each structure, the angle subtended at Zn(II), O(3)-Zn(II)-O(3) is 119.9(3)$^{\circ}$ for $Tl_{3.4}Zn_{4.3}-A$, and 120.0(3)$^{\circ}$ for $Tl_{5.5}Zn_{3.25}-A$, respectively, close to the idealized trigonal-planar value. Zn(II) ions prefer to 6-ring sites. $Tl^+$ ions do not have any preference to a particular site but occupy simultaneously both at the 6-ring sites and 8-ring sites.